CA1206300A - Polymerization of styrene - Google Patents
Polymerization of styreneInfo
- Publication number
- CA1206300A CA1206300A CA000425093A CA425093A CA1206300A CA 1206300 A CA1206300 A CA 1206300A CA 000425093 A CA000425093 A CA 000425093A CA 425093 A CA425093 A CA 425093A CA 1206300 A CA1206300 A CA 1206300A
- Authority
- CA
- Canada
- Prior art keywords
- styrene
- stream
- weight
- parts
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 title claims description 6
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical class CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 125000001979 organolithium group Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 150000002900 organolithium compounds Chemical class 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims description 2
- 230000003134 recirculating effect Effects 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 abstract description 10
- 229920002223 polystyrene Polymers 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000006203 ethylation Effects 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
- C08F4/48—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A polystyrene is prepared from a C8 cracker stream by first hydrogenating phenylacetylene to styrene and subsequently anionically polymerizing the styrene.
A polystyrene is prepared from a C8 cracker stream by first hydrogenating phenylacetylene to styrene and subsequently anionically polymerizing the styrene.
Description
~2~3~
ANIONIC POLYMERIZATION
OF Cl~ACKER STREAM STYRENE
For many years polystyrene has been a desired item of commerce. The polystyrenes commercially available range from relatively low molecular weight, brittle materials used in formulation of paints, and lacquers to higher molecular weight products suitable for moldings.
The polystyrene market is highly competitive, particularly in the field of molding and extrusion resins. Therefore, it is desirable that a process used to prepare such polymers should provide the desired results at minimal cost in time, energy, and processing equipment.
Styrene monomer has been prepared by ethylation of benzene followed by dehydrogenation and purification to polymerization grade styrene; that is, a styrene of sufficient purity to pol~merize readily to a generally water-white polymer. One attempt at providing a more economical route to polystyrene is set forth in Twaddle et al, U.S. Patent 2,813,089. In the Twaddle et al.
patent, a process is disclosed wherein aromatic C~ cut from the cracking of petroleum provides a mixture consisting primarily of xylenes and ethylbenzene which is subsequently dehydrogenated to provide a mixture of 29,483-F -1-. ., 3~
styrene and three isomers of xylene. This stream is then treated with metallic sodium to polymerize the styrene; the stream is filtered, devolatilized and the polystyrene recovered.
It is an object of this invention to provide an improved process for the preparation of polystyrene from a petroleum byproduct stream, and particularly for the preparation of styrene polymers of molding grade quantity in a direct manner from a petroleum byproduct stream.
The present invention is a process for the preparation o styrene polymers from a petroleum byproduct stream from the cracking of petroleum products, the stream cont~' ni ng pximarily C8 compounds and of an aromatic nature, and comprising 30 to 60 parts by weight styrene, 40 to 70 parts by weight of mixed isomers of xylene, and 0.5 to 2 parts by weight of phenylacetylene, characterized by hydrogenating at least a major portion of the phenylacetylene in the stream to styrene, polymerizing the styrene in the stream with an organolithium initiator whereby at least 99 percent of the styr~ne in the stream is converted to polymer, and recovering styrene polymer therefrom.
Advantageously, the polymerization is carried out in a continuously stirred tank reactor.
Cracker streams suitable for the practice of the present invention are generally those obtained from the C8 cut in the cracking of petroleum to prepare gasoline. Generally, the only component harmful to the polymerization of the styrene in such a stream is phenylacetylene which acting as a chain transfer agent 29,483-F -2--~ _3_ results in polymers that have a molecular weight too low to be useful in the molding and extrusion fields.
Phenylacetylene can be removed from such crack~r streams by selective hydrogenation since it is more readily hydrogenated than styrene. If the hydrog-enation is carefully done and preferably monitored by a gas chromatograph, the phenylacetylene can be selectively hydrogenated to styrene. Such hydrogenation may be done employing conventional hydrogenation techniques.
The hydrogenation may be high pressure or low pressure depending on the catalyst selected. Suitable catalysts include Raney nickel, platinum, palladium, ruthenium, rhodium, and copper chromite. The par~icular mode of hydrogenation will depend primarily on materlals and equipment most readily available or economically desirable.
The organolithium compounds employed in the practice of the present~invention are well known in the art, and are disclosed in the following U.S. Patents:
3,6~0,536; 3;663,634; 3,568,263; 3,684,780; 3,725,368;
3,734,973; 3,776,893; 3,776,964; 3,784,637; 3,787,510;
3,g54,894; 4,172,100; 4,172,190; 4,182,818; ~,196,153;
4,196,154; 4,200,718; 4,201,729; and 4,205,016.
Generally, for molding and extrusion, poly-styrene having a weight average molecular weight in the range o~ 150,000 to 300,000 gram moles is desired. The molecular weight is controlled by using the appropriate quantity of organolithium initiator. It is desirable that the amount of organolithium initiator be as low as possible as residual lithium compounds in polystyrene tend to contribute to a yellow coloration. To prepare 29,483-F -3-. .
63~
--4~
a polymer in the range of 150,000 to 350,000 weight average mol~cular welght ln a plug flow reactor requires between about 300 to 500 parts per million of n-butyl-lithium resulting in a polymer having a definite yellowish or amber cast. Employing the present invention usiny a continuously stirred tank reactor, only 100 to 150 parts per million of n-butyllithium are required resulting in a polymer that appears to be water-white, that is, transparent with no visible coloration.
Reactors particularly suitable for the presen-t invention are the so-called continuously stirred tank reactors. By the term "continuously stirred tank reactor" is meant a reactor in which a stream to be processed is continuously mixed to maintain the compo-sition within the reactor generally constant. Such a tank reactor may have a variety of configurations; for example, a cylindrical reactor having a dished head and bottom which is provided with an agitator capable of circulating the contents of the reactor around the periphery and vertically. Also useful as a continuously stirred tank reactor is the so-called coil reactor which comprises basically a recirculating loop, the loop having a pump which circulates the contents of the loop at a rate sufficiently rapid that no significant compositional variation is detected if the loop is sampled at different locations. Sui-table reactors are set forth in U.S. Patents: 2,745,824; 2,989,517;
3,035,933; 3,747,899 and 3,765,655.
The present invention is further illustrated but no-t limited by the following example.
29,483-F _4_ ~ti3~3~
Example A C8 cut from the distillation of pyrolosls gasoline was analyzed by a gas chromatograph and found to contain 46.96 weight percent xylene, 50.33 weight percent styrene and 0.74 weight percent phenylacetylene.
The rem~ining fraction of the stream was a variety of generally nonreactive C8 compounds. 900 Milliliters of the C8 cut were placed in a 3-liter flask equipped with a magnetic stirrer and a hydrogen inlet and outlet.
30 Grams of a carbon supported palladium catalyst were added to the flask. The flask was then flushed with hydrogen and the conkents of the flask were agitated with the magnetic stirrer. The temperature of the reaction mixture was about 25C. The contents of the flask were analyzed by gas chromatograph at 10 minute intervals to detect the presence of phenylacetylene.
After a period of 50 minutes, the gas chromatograph indicated no detectable phenylacetylene with 47.41 weight percent xylene, and 50.~8 weight percent styrene.
The filtered reaction mixture was distilled through a 1220 cm by 2.5 cm (48 inch by 1 inch) under a pressure of 50 millimeters of-mercuxy employing a 3-1 reflux ratio. The firs-t 50 milliliters of distillate were discarded.
200 Milliliters of the distillate were charged to a dry round bottom flask fitted with an agitator and an opening closed by a rubber septum. Employed in the distillate were titrate with a 1 n solution of n-butyl-lithium in cyclohexane until a slight reddish color persis-ted in the contents of the flaskO 1.8 Centimeters of the n-butyllithium solution were required. An additional 1.3 milliliters of the n~butyllithium solution 29,483-F -5-';
631~
were added. Polymerization of the contents occurred over a period of about 20 minutes and the conten-ts of the flask reached a temperature of 80C. The polymer was recovered and devolatiliæed. Gel permeation chromatograph of the polystyrene obtained a weight average molecular weight of 160,000 gram moles, a normal average molecular weight of 90,000. From the amount of lithium initiator added, the theoretical average molecular weight was 100,000.
The present invention is susceptible of being embodied with various alterations and modifications which may differ particularly from those that have been described in the preceding specification and description.
29,483-F -6-
ANIONIC POLYMERIZATION
OF Cl~ACKER STREAM STYRENE
For many years polystyrene has been a desired item of commerce. The polystyrenes commercially available range from relatively low molecular weight, brittle materials used in formulation of paints, and lacquers to higher molecular weight products suitable for moldings.
The polystyrene market is highly competitive, particularly in the field of molding and extrusion resins. Therefore, it is desirable that a process used to prepare such polymers should provide the desired results at minimal cost in time, energy, and processing equipment.
Styrene monomer has been prepared by ethylation of benzene followed by dehydrogenation and purification to polymerization grade styrene; that is, a styrene of sufficient purity to pol~merize readily to a generally water-white polymer. One attempt at providing a more economical route to polystyrene is set forth in Twaddle et al, U.S. Patent 2,813,089. In the Twaddle et al.
patent, a process is disclosed wherein aromatic C~ cut from the cracking of petroleum provides a mixture consisting primarily of xylenes and ethylbenzene which is subsequently dehydrogenated to provide a mixture of 29,483-F -1-. ., 3~
styrene and three isomers of xylene. This stream is then treated with metallic sodium to polymerize the styrene; the stream is filtered, devolatilized and the polystyrene recovered.
It is an object of this invention to provide an improved process for the preparation of polystyrene from a petroleum byproduct stream, and particularly for the preparation of styrene polymers of molding grade quantity in a direct manner from a petroleum byproduct stream.
The present invention is a process for the preparation o styrene polymers from a petroleum byproduct stream from the cracking of petroleum products, the stream cont~' ni ng pximarily C8 compounds and of an aromatic nature, and comprising 30 to 60 parts by weight styrene, 40 to 70 parts by weight of mixed isomers of xylene, and 0.5 to 2 parts by weight of phenylacetylene, characterized by hydrogenating at least a major portion of the phenylacetylene in the stream to styrene, polymerizing the styrene in the stream with an organolithium initiator whereby at least 99 percent of the styr~ne in the stream is converted to polymer, and recovering styrene polymer therefrom.
Advantageously, the polymerization is carried out in a continuously stirred tank reactor.
Cracker streams suitable for the practice of the present invention are generally those obtained from the C8 cut in the cracking of petroleum to prepare gasoline. Generally, the only component harmful to the polymerization of the styrene in such a stream is phenylacetylene which acting as a chain transfer agent 29,483-F -2--~ _3_ results in polymers that have a molecular weight too low to be useful in the molding and extrusion fields.
Phenylacetylene can be removed from such crack~r streams by selective hydrogenation since it is more readily hydrogenated than styrene. If the hydrog-enation is carefully done and preferably monitored by a gas chromatograph, the phenylacetylene can be selectively hydrogenated to styrene. Such hydrogenation may be done employing conventional hydrogenation techniques.
The hydrogenation may be high pressure or low pressure depending on the catalyst selected. Suitable catalysts include Raney nickel, platinum, palladium, ruthenium, rhodium, and copper chromite. The par~icular mode of hydrogenation will depend primarily on materlals and equipment most readily available or economically desirable.
The organolithium compounds employed in the practice of the present~invention are well known in the art, and are disclosed in the following U.S. Patents:
3,6~0,536; 3;663,634; 3,568,263; 3,684,780; 3,725,368;
3,734,973; 3,776,893; 3,776,964; 3,784,637; 3,787,510;
3,g54,894; 4,172,100; 4,172,190; 4,182,818; ~,196,153;
4,196,154; 4,200,718; 4,201,729; and 4,205,016.
Generally, for molding and extrusion, poly-styrene having a weight average molecular weight in the range o~ 150,000 to 300,000 gram moles is desired. The molecular weight is controlled by using the appropriate quantity of organolithium initiator. It is desirable that the amount of organolithium initiator be as low as possible as residual lithium compounds in polystyrene tend to contribute to a yellow coloration. To prepare 29,483-F -3-. .
63~
--4~
a polymer in the range of 150,000 to 350,000 weight average mol~cular welght ln a plug flow reactor requires between about 300 to 500 parts per million of n-butyl-lithium resulting in a polymer having a definite yellowish or amber cast. Employing the present invention usiny a continuously stirred tank reactor, only 100 to 150 parts per million of n-butyllithium are required resulting in a polymer that appears to be water-white, that is, transparent with no visible coloration.
Reactors particularly suitable for the presen-t invention are the so-called continuously stirred tank reactors. By the term "continuously stirred tank reactor" is meant a reactor in which a stream to be processed is continuously mixed to maintain the compo-sition within the reactor generally constant. Such a tank reactor may have a variety of configurations; for example, a cylindrical reactor having a dished head and bottom which is provided with an agitator capable of circulating the contents of the reactor around the periphery and vertically. Also useful as a continuously stirred tank reactor is the so-called coil reactor which comprises basically a recirculating loop, the loop having a pump which circulates the contents of the loop at a rate sufficiently rapid that no significant compositional variation is detected if the loop is sampled at different locations. Sui-table reactors are set forth in U.S. Patents: 2,745,824; 2,989,517;
3,035,933; 3,747,899 and 3,765,655.
The present invention is further illustrated but no-t limited by the following example.
29,483-F _4_ ~ti3~3~
Example A C8 cut from the distillation of pyrolosls gasoline was analyzed by a gas chromatograph and found to contain 46.96 weight percent xylene, 50.33 weight percent styrene and 0.74 weight percent phenylacetylene.
The rem~ining fraction of the stream was a variety of generally nonreactive C8 compounds. 900 Milliliters of the C8 cut were placed in a 3-liter flask equipped with a magnetic stirrer and a hydrogen inlet and outlet.
30 Grams of a carbon supported palladium catalyst were added to the flask. The flask was then flushed with hydrogen and the conkents of the flask were agitated with the magnetic stirrer. The temperature of the reaction mixture was about 25C. The contents of the flask were analyzed by gas chromatograph at 10 minute intervals to detect the presence of phenylacetylene.
After a period of 50 minutes, the gas chromatograph indicated no detectable phenylacetylene with 47.41 weight percent xylene, and 50.~8 weight percent styrene.
The filtered reaction mixture was distilled through a 1220 cm by 2.5 cm (48 inch by 1 inch) under a pressure of 50 millimeters of-mercuxy employing a 3-1 reflux ratio. The firs-t 50 milliliters of distillate were discarded.
200 Milliliters of the distillate were charged to a dry round bottom flask fitted with an agitator and an opening closed by a rubber septum. Employed in the distillate were titrate with a 1 n solution of n-butyl-lithium in cyclohexane until a slight reddish color persis-ted in the contents of the flaskO 1.8 Centimeters of the n-butyllithium solution were required. An additional 1.3 milliliters of the n~butyllithium solution 29,483-F -5-';
631~
were added. Polymerization of the contents occurred over a period of about 20 minutes and the conten-ts of the flask reached a temperature of 80C. The polymer was recovered and devolatiliæed. Gel permeation chromatograph of the polystyrene obtained a weight average molecular weight of 160,000 gram moles, a normal average molecular weight of 90,000. From the amount of lithium initiator added, the theoretical average molecular weight was 100,000.
The present invention is susceptible of being embodied with various alterations and modifications which may differ particularly from those that have been described in the preceding specification and description.
29,483-F -6-
Claims (5)
1. A process for the preparation of styrene polymers from a petroleum byproduct stream from the cracking of petroleum products, the stream containing primarily C8 compounds and of an aromatic nature and comprising 30 to 60 parts by weight styrene, 40 to 70 parts by weight of mixed isomers of xylene, and 0.5 to 2 parts by weight of phenylacetylene, characterized by hydrogenating at least a major portion of the phenyl-acetylene in the stream to styrene, polymerizing the styrene in the stream with an organolithium initiator whereby at least 99 percent of the styrene in the stream is converted to polymer, and recovering the styrene polymer.
2. The process of Claim 1 wherein the polymerization is carried out in a continuously stirred tank reactor.
3. The method of Claim 1 wherein phenyl-acetylene is hydrogenated employing a palladium catalyst.
4. The method of Claim 1 wherein the organo-lithium compound is n-butyllithium.
5. The process of Claim 1 wherein the reactor has the configuration of a recirculating loop.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US364,958 | 1982-04-02 | ||
| US06/364,958 US4389517A (en) | 1982-04-02 | 1982-04-02 | Hydrogenation of phenylacetylene prior to styrene polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1206300A true CA1206300A (en) | 1986-06-17 |
Family
ID=23436869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000425093A Expired CA1206300A (en) | 1982-04-02 | 1983-03-31 | Polymerization of styrene |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4389517A (en) |
| EP (1) | EP0091101A3 (en) |
| JP (1) | JPS58201808A (en) |
| KR (1) | KR910005660B1 (en) |
| AU (1) | AU563600B2 (en) |
| CA (1) | CA1206300A (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2603578B1 (en) * | 1986-09-10 | 1989-02-17 | Inst Francais Du Petrole | PROCESS FOR SELECTIVE HYDROGENATION OF PHENYL-ACETYLENE IN A STYRENE-RICH CUT |
| US4822936A (en) * | 1987-08-25 | 1989-04-18 | The Dow Chemical Company | Selective hydrogenation of phenylacetylene in the presence of styrene |
| AU628194B2 (en) * | 1989-07-28 | 1992-09-10 | Idemitsu Kosan Co. Ltd | Process for producing styrene polymers |
| US5064918A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Ziegler-Natta polymerization of styrene monomer |
| EP0417724B1 (en) * | 1989-09-14 | 1996-05-15 | The Dow Chemical Company | Coordination polymerization of styrene monomer |
| ATE138630T1 (en) * | 1991-10-10 | 1996-06-15 | Dow Chemical Co | METHOD FOR SELECTIVE HYDROGENATION OF AROMATIC ACETYLENE COMPOUNDS |
| US5637650A (en) | 1996-06-14 | 1997-06-10 | Ferro Corporation | Brominated polysytrene having improved thermal stability and color and process for the preparation thereof |
| US6518368B2 (en) | 1996-06-14 | 2003-02-11 | Albemarle Corporation | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof |
| US6326439B1 (en) | 1996-09-26 | 2001-12-04 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US6232408B1 (en) | 1996-09-26 | 2001-05-15 | Albemarle Corporation | Brominated polstyrenic resins |
| US5767203A (en) * | 1996-09-26 | 1998-06-16 | Albemarle Corporation | Process for brominated styrenic polymers |
| US6235831B1 (en) | 1996-09-26 | 2001-05-22 | Albemarle Corporation | Polymer compositions containing brominated polystyrenic resins |
| US6235844B1 (en) | 1996-09-26 | 2001-05-22 | Albemarle Corporation | Brominated polystyrenic resins |
| US6521714B2 (en) | 1996-09-26 | 2003-02-18 | Albemarle Corporation | Brominated polystyrenic resins |
| US6232393B1 (en) | 1996-09-26 | 2001-05-15 | Albemarle Corporation | Polymers flame retarded with brominated polystyrenic resins |
| US5677390A (en) * | 1996-09-26 | 1997-10-14 | Albemarle Corporation | Process for brominating polystyrenic resins |
| US5686538A (en) * | 1996-09-26 | 1997-11-11 | Albemarle Corporation | Process for brominating polystyrenic resins |
| DE69701997T2 (en) | 1996-09-26 | 2000-11-09 | Albemarle Corp., Baton Rouge | METHOD FOR BROWNING STYRENE POLYMERS |
| US6133381A (en) * | 1996-09-26 | 2000-10-17 | Albelmarle Corporation | Brominated polystyrenic flame retardants |
| EP0834499B1 (en) * | 1996-10-02 | 2001-07-25 | Dainippon Ink And Chemicals, Inc. | Process for the preparation of aromatic vinyl compounds |
| US6440230B1 (en) | 2000-03-03 | 2002-08-27 | Micron Technology, Inc. | Nitride layer forming method |
| US6979717B2 (en) * | 2001-08-13 | 2005-12-27 | Moore Eugene R | Anionic process design for rapid polymerization of polystyrene without gel formation and product produced there from |
| US7244868B2 (en) * | 2002-06-25 | 2007-07-17 | Shell Oil Company | Process for the dehydrogenation of an unsaturated hydrocarbon |
| US7105711B2 (en) * | 2003-07-31 | 2006-09-12 | Fina Technology, Inc. | Process for the selective hydrogenation of phenylacetylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2813089A (en) * | 1955-07-21 | 1957-11-12 | Standard Oil Co | Direct production of polystyrene from petroleum by-product ethylbenzene |
-
1982
- 1982-04-02 US US06/364,958 patent/US4389517A/en not_active Expired - Lifetime
-
1983
- 1983-03-25 AU AU12854/83A patent/AU563600B2/en not_active Ceased
- 1983-03-31 CA CA000425093A patent/CA1206300A/en not_active Expired
- 1983-03-31 EP EP83103220A patent/EP0091101A3/en not_active Withdrawn
- 1983-04-01 JP JP58055325A patent/JPS58201808A/en active Pending
- 1983-04-02 KR KR1019830001378A patent/KR910005660B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58201808A (en) | 1983-11-24 |
| EP0091101A3 (en) | 1985-01-09 |
| KR910005660B1 (en) | 1991-08-01 |
| US4389517A (en) | 1983-06-21 |
| AU1285483A (en) | 1983-10-06 |
| KR840004445A (en) | 1984-10-15 |
| AU563600B2 (en) | 1987-07-16 |
| EP0091101A2 (en) | 1983-10-12 |
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